无铅焊料用水基无卤无VOC助焊剂

采用无卤素有机酸和有机胺作为活化剂,以去离子水为溶剂,并添加非离子表面活性剂,通过铺展率实验对各主要成分及配比进行选择和优化设计,研究了一种无铅焊料用水基无卤无VOC助焊剂。依据电子行业标准对研制的助焊剂进行了性能测试。结果表明,制备的助焊剂不含卤素、VOC物质,对无铅焊料的润湿性强,焊点光亮饱满,焊后残留少,铺展率可达78.2%,适用于SnAgCu和SnCu无铅焊料的波峰焊。     

纳米颗粒增强无铅复合焊料的研究现状

熔化温度、润湿性及长期使用过程中的可靠性决定了无铅焊料的应用范围.通过添加适量纳米颗粒可显著提高无铅焊料的性能,特别是添加适量纳米Ag颗粒后SnCu焊料蠕变断裂寿命是未添加时的13倍.介绍了添加纳米颗粒对无铅焊料的物理化学性能的影响;探讨了纳米颗粒增强无铅复合焊料微观结构和力学性能;展望了纳米颗粒增强手段对焊料应用的前...     

颗粒增强Sn-Ag基无铅复合钎料显微组织与性能

通过外加法向Sn-3.5Ag焊料中加入体积分数为10%的微米级Cu、Ni颗粒制备了无铅复合钎料,对钎料的显微组织、拉剪及润湿性能进行了研究。结果表明,颗粒周围以及基板界面处的显微组织中生成了金属间化合物,其形态及大小因加入颗粒而不同。颗粒的加入提高了钎料钎焊接头的剪切强度,其中Cu颗粒增强的接头的剪切强度提高了33%,Ni颗粒的提高了20%。两种复合钎料的铺展面积均下降了约15%,其中Cu颗粒增强复合钎料润湿角由11°增加到18°。     

New,lead-free solders

Two specific examples of the new lead-free alloys are described. In the Sn-3.5%Ag-l%Zn alloy (m.p.~217°C), the eutectic precipitate morphology is refined by the relatively small amount of zinc addition and as a result, a high-strength, high-ductility solder with significantly improved creep resistance is obtained. As a temperature equivalent drop-in replacement for the Pb-Sn eutectic alloy (m.p.~183°C), Sn-Zn-In based alloys (m.p.~185°C) have been developed. The addition of indium to the Sn-Zn binary system improves the wetting characteristics of the alloy and lowers the melting temperature.     

电子组装用高温无铅钎料的研究进展

分析了国内外电子组装用高温无铅钎料的研究现状。指出目前常用的高温钎料仍然是高Pb焊料或80Au-20Sn钎料,导致焊料含Pb而污染环境,或者含质量分数为80%的Au而使焊料成本奇高。指明了Bi-Ag系钎料具有潜力替代高Pb焊料或80Au-20Sn钎料。未来的研究将在成分设计及可靠性等方面进行探索,以最终找到既经济又可替代传统高铅钎料的高温无铅钎料。     

Effect of flux on the wetting characteristics of SnAg, SnCu, SnAgBi, and SnAgCu lead-free solders on copper substrates

The effect of flux on the wetting characteristics of four lead-free solders, Sn-3.5Ag, Sn-0.7Cu, Sn-3.5Ag-4.8Bi, and Sn-3.8Ag-0.7Cu (wt.%), on copper substrates have been studied at 240, 260, and 280°C. The fluxes investigated were rosin (R), mildly activated rosin (RMA), and activated rosin (RA). The wetting tests were conducted using the sessile-drop method. Results showed that fluxes significantly affect the wetting properties of the solders. Contact angles ranging from 10° to 30° for RMA, 20° to 30° for RA, and 35° to 60° for R were obtained. The effect of temperature on contact angle depended on the type of flux used. The contact angle decreased with increasing temperature; however, in some cases the contact angle was independent of temperature. The Sn-3.5Ag-4.8Bi exhibited the lowest contact angles indicating improved wettability with addition of bismuth. The microstructure of the solder/copper interface was analyzed by scanning electron microscopy.     

三种高Sn无铅钎料的表面张力和润湿性能研究

采用悬滴法测量了3种无铅钎料合金(Sn-3.0Ag-0.5Cu、Sn-0.7Cu与Sn-9.0Zn)在260℃时的表面张力,分别为525.5,534.8和595.4 mN/m;同时采用座滴法测量了其在260℃熔融状态下与Cu基板的接触角,分别为24.5°、28.0°和102.5°,并且与传统Sn-37.0Pb钎料进行了比较研究。结果表明,无铅钎料合金的表面张力与接触角均大于Sn-37.0Pb钎料。结合Young-Dupre公式讨论了钎料合金表面张力与其润湿性能的相关性,认为Sn基钎料合金在Cu基板上的润湿性能主要取决于其表面张力。     

Creep phenomena in lead-free solders

A critical review of data on microstructure and creep process activation energy values for a number of lead-free solder alloys like Sn-Ag; Sn-Bi; Sn-In was conducted. The review revealed a scatter in experimental data, which could not be explained by the dislocation creep mechanism only, even after the published data was corrected for Young’s modulus temperature dependence. An analysis of the data implies that possible origin of such a scatter is nucleation, accumulation and further growth of such internal defects as pores and microcracks during creep. It is shown that these processes may affect the measured steady-state creep rates, and may be one of the major reasons for the observed scatter in experimental data, and, therefore, must be taken into consideration in lead-free solder alloys’ creep studies.     

Reactions of lead-free solders with CuNi metallizations

We have done experimental research on the dissolution rate and intermetallic growth on Cu, Ni, and CuNi-alloy substrates as a function of time and Cu/Ni ratio of the substrate. Reactions that occur when CuNi metallizations are soldered with lead-free solders were investigated. The experiments were performed using Sn-3.5Ag and Sn-3.8Ag-0.7Cu solders and different CuNi alloys. To determine the rate of dissolution of the substrate material into the solder, CuNi foils of different concentrations were immersed in Sn-3.5Ag and Sn-3.8Ag-0.7Cu solder baths for soldering times ranging from 15 sec to 5 min at 250°C. In addition, reflows of solder balls were made on top of bulk substrates to study the reaction when there is a practically infinite amount of CuNi available compared to the amount of solder. Thin film experiments were also done, where Ni containing under bump metallizations (UBMs) were fabricated and reflowed with eutectic SnAg solder balls. The nickel slows down the dissolution of the UBM into the solder and the formation of intermetallics during reflow compared to Cu metallizations. The solder/UBM interfaces were analyzed with SEM to find out how Ni concentration affects the reaction, and how much Ni is needed to obtain a sufficiently slow reaction rate.     

Resonant vibration behavior of lead-free solders

This study investigated the resonant vibration-fatigue characteristics of some potential lead-free solders, including Sn-Zn, Sn-Ag Sn-Cu, and Sn-Bi alloys. Results show that, under a fixed vibration force, the damping capacity and vibration-fracture resistance of Sn-Cu and Sn-Ag eutectic alloys with an off-eutectic structure are higher than Sn-Pb and are also higher than Sn-Bi and Sn-Zn. This is closely related to the vibration-deformed structure and crack-propagation morphology associated with the microstructural features of the materials. Also, the striated deformation in the Sn-rich phase can be regarded as an effective mechanism in absorbing vibration energy. Moreover, microstructural modification of the Sn-Zn eutectic alloy can be achieved through Ag addition, and thus, the damping capacity and vibration-fracture resistance can be significantly improved.     

Contact angle measurements of Sn-Ag and Sn-Cu lead-free solders on copper substrates

In this study, the contact angles of four lead-free solders, namely, Sn-3.5Ag, Sn-3.5Ag-4.8Bi, Sn-3.8Ag-0.7Cu, and Sn-0.7Cu (wt.%), were measured on copper substrates at different temperatures. Measurements were performed using the sessile-drop method. Contact angles ranging from 30° to 40° after wetting under vacuum with no fluxes and between 10° and 30° with rosin mildly activated (RMA) and rosin activated (RA) fluxes were obtained. The Sn-3.5Ag-4.8Bi exhibited the lowest contact angles, indicating improved wettability with the addition of bismuth. For all soldering alloys, lower contact angles were observed using RMA flux. Intermetallics formed at the solder/Cu interface were identified as Cu₆Sn₅ adjacent to the solder and Cu₃Sn adjacent to the copper substrate. The Cu₃Sn intermetallic phase was generally not observed when RMA flux was used. The effect of temperature on contact angle was dependent on the type of flux used.     

In search of new lead-free electronic solders

Tin-lead solder has been widely used in the electronics industry for many years. However, increasing environmental pressures, together with some technological issues, have now prompted great interest in finding a viable nonleaded substitute. This paper first summarizes some of the background issues, specifically availability, cost, and toxicity. It then outlines some of the work undertaken by Cookson Group plc on behalf of Alpha-Fry in searching for alloys with a narrow melting range between 135 and 183°C.     

Wetting interaction of Pb-free Sn-Zn-Al solders on metal plated substrate

A newly developed Pb-free Sn-9(Zn-5Al) solder was investigated for its wetting behavior on metal plated Cu substrate. The Cu substrate was plated with electroless nickel (EN) or with EN/Cu multilayer plating. The wetting behavior was investigated with a wetting balance which gave rise to a wetting curve. Fluxes including L-glutamic acid and dimethylammonium chloride were applied for enhancing the wetting behavior. The solder was unable to wet the EN plated Cu substrate without the assistance of flux until temperatures of 460°C and above. The material interaction between the solder and the substrate at this high temperature was investigated with scanning electron microscope elemental analysis. The wetting temperature between solder and EN plated copper was lowered to 310°C with the application of the above fluxes. The further incorporation of a layer of Cu plating with the EN layer further lowered the wetting temperature to 250°C.     

Characterization of the growth of intermetallic interfacial layers of Sn-Ag and Sn-Pb eutectic solders and their composite solders on Cu substrate during isothermal long-term aging

Single shear lap joints were made with four different solders, Sn-Pb and Sn-Ag eutectic solders, and their composites containing about 20 vol.% in-situ Cu6Sn5 intermetallic phases about 3–8 micrometers in diameter. Two sets of experiments were performed: In the first set, all of the above four solder joints were aged at 150°C for periods ranging to 5000 h and the intermetallic growth was monitored periodically. In the second set, each of the above four solder joints was aged at five different temperatures for 4000 h. The interfacial layers between solders and the Cu substrate were examined using optical and scanning electron microscopy. The growth kinetics of intermetallic interfacial layers formed between solder and Cu substrate was characterized. The effect of in-situ Cu₆Sn₅ intermetallic phases on the growth rate is discussed. The growth rate of the intermetallic layers in the eutectic Sn-Pb composite was slower for the first 150 h as compared to the eutectic Sn-Pb non-composite. The growth rate of the intermetallic layers were similar for both the eutectic Sn-Ag and eutectic Sn-Ag composite throughout the aging duration. The activation energies for Cu₆Sn₅ layer growth for the eutectic Sn-Pb and Sn-Ag solder joints are evaluated to be 111 kJ/mol and 116 kJ/mol, respectively. The eutectic Sn-Pb and Sn-Ag composite solder joints exhibit higher activation energies of 161 kJ/mol and 203 kJ/mol.     

Investigation of multi-component lead-free solders

Binary phase diagrams of interest for lead-free solder development have been entered into the THERMO-CALC data base. These may be used directly to calculate multi-component phase relations vs temperature provided there are no ternary or higher order interactions. Such occur in the Sn-Ag-Zn system and are being evaluated. Contact angles of a number of solder-flux combinations on copper were directly measured in spreading tests. With a rosin-isopropyl alcohol flux, the contact angles of binary eutectic solders were in degrees: Sn-Bi at 166°C, 40; Sn-Zn at 225°C, 60; Sn-Ag at 250°C, 45. These angles were little affected by a number of 1% ternary additions to the solder. The contact angles were 20 degrees or less when SnCl₂ was used as a flux. The SnCl₂ reacts with Cu to form Cu₃Sn. The most likely successful approach to obtain satisfactory wetting with lead-free solders appears to be development of a satisfactory flux.     

Intermetallic growth between lead-free solders and palladium

Intermetallic growth between Pd and the lead-free solders Sn-Ag and Sn-Ag-Cu has been studied. Diffusion couples were prepared by reflowing the solders on Pd and then aging the couples at 156°C, 175°C, 195°C, and 210°C. At the higher temperatures of 175°C, 195°C, and 210°C, PdSn₄ made up most of the layer that grew between the solders and the Pd, although small regions of second phases were always found in the PdSn₄ matrix, and it was sometimes possible to identify discontinuous regions of PdSn₃ next to the Pd. The thickness of the intermetallic layer increased with the square root of time, consistent with diffusion-controlled growth. In couples annealed at 156°C, the morphology of the PdSn₃ phase and growth kinetics differed depending on the composition of the solder.     

Interfacial reactions of Cu-containing lead-free solders with Au/NiP metallization

Cu-containing solder alloys have been used to identify their interfacial reactions with electroless NiP. As-reflowed, AuSn₄ intermetallic compounds (IMCs) are formed in the Sn-Cu and Sn-Ag-Cu solders, but in the cases of Sn-Ag-Cu-In, In-Sn-Au IMCs are formed and are uniformly distributed in the solder. Different types of IMCs such as high-Cu (>30 at.%), medium-Cu (30-15 at.%), and low-Cu (<15 at.%) containing IMCs are formed at the interface. High-Cu and medium-Cu containing ternary intermetallic compounds (TIMCs) are found in the Sn-Cu and Sn-Ag-Cu solder joints, respectively. Medium-Cu containing quaternary intermetallic compounds (QIMCs) are found in the Sn-Ag-Cu-In joints. Initially, TIMCs and QIMCs have higher growth rates, resulting in the entrapment of some Pb-rich phase in the high-Cu containing TIMCs and some In-Sn-Au phase in the QIMCs. High-Cu containing TIMCs have a lower growth rate and consume less of the NiP layer. The spalling of medium-Cu containing TIMCs in the Sn-Ag-Cu solder increases both the growth rate of TIMCs and the consumption rate of the NiP layer. Low-Cu containing QIMCs in the Sn-Ag-Cu-In solder are stable on P-rich Ni and reduce the dissolution rate of the NiP layer. Consumption of the NiP layer can be reduced by adding Cu or In, because of the changes of the interfacial IMCs phases, which are stable and adhere well to the P-rich Ni layer during reflow.     

The characteristics of vibration fracture of Pb-Sn and lead-free Sn-Zn eutectic solders

This work investigated the fatigue fracture characteristics of Sn-7∼11wt.%Zn and Sn-30∼50wt.%PPb solder alloys under resonant vibration. For the alloys containing proeutectic Sn-rich grains, the results show stratum appearance on the deformation of coarse proeutectic grains. This stratum-type deformation will reduce the vibration resistance of Pb-Sn solder by inducing cracks. For the Sn-Zn system, fine eutectic structure will cause cracks to form and coalesce easily in the regions concentrated with small fibrous deformation grains, whereas hypereutectic structure shows coarse proeutectic Zn-rich particles as the crack initiation sites. Sn-t-Zn solders have better damping capacity than Pb-Sn solders. With hypoeutectic composition to induce stratum-type deformation and under lower vibration strain, these lead-free solders tend to exhibit superior crack propagation resistance, and, in that respect, are possible to replace Pb-Sn solders.     

Wetting interaction between Sn-Zn-Ag solders and Cu

The wetting interaction of Sn-(7.1–9)Zn-(0–3)Ag solders with Cu was investigated from 230°C to 300°C. The wetting time, wetting forces, and activation energy of the wetting reaction were studied. The wetting time decreases with increasing temperature and increases with Ag content. The wetting force exhibits a disproportional correlation to temperature rise, while no trend was observed with respect to Ag content. The wetting behavior was ascribed to the interaction between Cu and Zn. The AgZn₃ compound was formed at the interface when the solder contains 0.3% Ag and above, while it was formed within the bulk solder at 2% Ag and above.     

Sn-Cu系无松香无卤免清洗助焊剂研制

将低沸点与高沸点的有机酸进行复配,添加沸点接近波峰焊温度的混合溶剂及其他添加剂,得到了一种用于Sn-Cu系波峰焊无铅焊锡的助焊剂。测试结果表明:当丁二酸、衣康酸、己二酸、三异丙醇胺的质量比为4∶2∶3∶1,有机酸活化剂质量分数为5%,表面活性剂质量分数为0.15%,成膜剂质量分数为0.50%,有机溶剂质量分数为15%,余量为去离子水时,助焊剂溶液的pH值约为4,钎料焊后的铺展率接近于77%,焊点饱满光亮,对铜板腐蚀性小,焊后无残留,绝缘性良好。